Dual Recycling of Depolymerization Catalyst and Biodegradable Polyester that Markedly Outperforms Polyolefins.

Chemically recyclable, circular polymers continue to attract increasing attention, but rendering both catalysts for depolymerization and high-performance polymers recyclable is a more sustainable yet challenging goal. Here we introduce a dual catalyst/polymer recycling system in that recyclable inorganic phosphomolybdic acid catalyzes selective depolymerization of high-ceiling-temperature biodegradable poly(δ-valerolactone) in bulk phase, which, upon reaching suitable molecular weight, exhibits outstanding mechanical performance with a high tensile strength of ≈66.6 MPa, fracture strain of ≈904 %, and toughness of ≈308 MJ m-3 , and thus markedly outperforms commodity polyolefins, recovering its monomer in pure state and quantitative yield at only 100 °C. In sharp contrast, the uncatalyzed depolymerization not only requires a high temperature of >310 °C but is also low yielding and non-selective. Importantly, the recovered monomer can be repolymerized as is to reproduce the same polymer, thereby closing the circular loop, and the recycled catalyst can be reused repeatedly for depolymerization runs without loss of its catalytic activity and efficiency.

A circular polyester platform based on simple gem-disubstituted valerolactones.

Geminal disubstitution of cyclic monomers is an effective strategy to enhance the chemical recyclability of their polymers, but it is utilized for that purpose alone and often at the expense of performance properties. Here we present synergistic use of gem-α,α-disubstitution of available at-scale, bio-based δ-valerolactones to yield gem-dialkyl-substituted valerolactones ([Formula: see text]), which generate polymers that solve not only the poor chemical recyclability but also the low melting temperature and mechanical performance of the parent poly(δ-valerolactone); the gem-disubstituted polyesters ([Formula: see text]) therefore not only exhibit complete chemical recyclability but also thermal, mechanical and transport properties that rival or exceed those of polyethylene. Through a fundamental structure-property study that reveals intriguing impacts of the alkyl chain length on materials performance of [Formula: see text], this work establishes a simple circular, high-performance polyester platform based on [Formula: see text] and highlights the importance of synergistic utilization of gem-disubstitution for enhancing both chemical recyclability and materials performance of sustainable polyesters.

Mechanistic aspects of metal valence change in SalenCo(III)OAc-catalyzed hydrolytic kinetic resolution of racemic epoxides.

The chiral SalenCo(III)OAc-catalyzed hydrolytic kinetic resolution (HKR) of racemic terminal epoxides to afford both enantioenriched epoxides and diols presents one of the most important achievements in asymmetric synthesis chemistry. Previous studies mainly focused on the development of highly efficient catalysts, while rare reports concerned the mechanistic understanding of metal valence change, associated with the formation of inactive Co(II)-Salen complex. Herein, we report the mechanistic aspects of catalyst deactivation regarding the transformation of Co(III) to Co(II) derivative in the HKR of racemic epoxides catalyzed by SalenCo(III)OAc complexes with an appended 1,5,7-triazabicyclo[4.4.0]dec-5-ene on the ligand framework by means of electrospray ionization mass spectrometry (ESI-MS). Continuous determination of transient cationic species in ESI-MS positive mode in conjunction with UV-vis spectroscopic studies at various time points provides evidence that a certain amount of SalenCo(III)OAc molecules were reduced to the corresponding Co(II) derivatives in the HKR of racemic propylene oxide or styrene oxide. To be accompanied by the reduction of Co(III) to Co(II), the resultant diols were oxidized to α-hydroxy ketones. These analyses along with some control experiments gave a mechanistic understanding of catalyst deactivation of SalenCo(III)OAc-catalyzed HKR of racemic epoxides regarding an unveiled redox reaction between Co(III)-Salen and diol, the hydrolyzed product.